Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C263/00—Preparation of derivatives of isocyanic acid
  • C07C263/18—Separation; Purification; Stabilisation; Use of additives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C267/00—Carbodiimides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D229/00—Heterocyclic compounds containing rings of less than five members having two nitrogen atoms as the only ring hetero atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0025—Foam properties rigid

Definitions

• the invention relates to a new process for the preparation of liquid, storage-stable carbodiimide and / or uretonimine groups containing isocyanate mixtures, the mixtures obtainable by this process and their use in the production of polyurethane plastics, preferably polyurethane foams.
• Isocyanate mixtures containing carbodiimide and / or uretonimine groups can be prepared in a particularly simple manner using the catalysts from the phospholine oxide series, which are by far the most effective for this, according to the basic procedure of US Pat. No. 2,853,473.
• Anhydrous hydrochloric acid is said to have a sufficient deactivating effect (Angew. Chem. 93 , p. 859 (1981).
• DE-OS 2 614 323 discloses thionyl chloride as a preferred “deactivator”.
• the invention also relates to the liquid polyisocyanate mixtures which can be obtained by the process mentioned above.
• the invention also relates to the use of the liquid polyisocyanate mixtures according to the invention for the production of polyurethane plastics, preferably polyurethane foams with improved fire behavior.
• Any organic isocyanates can be used as starting materials for the process according to the invention.
• the process according to the invention is preferably used for the carbodiimidization of organic diisocyanates of the type used in polyurethane chemistry.
• the process according to the invention is carried out in the presence of the named highly effective catalysts from the phospholine series, for example a commercially available mixture of the phospholine oxides of the formulas:
• the amount of catalyst used depends on the quality of the starting isocyanates. It is therefore easiest to determine the amount of catalyst required in each case in a preliminary experiment.
• the carbodiimidization reaction is generally carried out in the temperature range between 50 to 150 ° C., preferably 60 to 100 ° C.
• the optimal reaction temperature depends on the type of starting isocyanates used and can be determined in a simple preliminary test.
• degree of carbodiimidization can be recognized during the process according to the invention from the amount of carbon dioxide escaping from the reaction mixture. This volumetrically determinable amount of carbon dioxide thus provides information about the degree of carbodiimidization achieved at all times during the process according to the invention.
• the additive essential to the invention is used as a stopper.
• the additives essential to the invention are silylated acids of the formula X- [Si (CH 3 ) 3 ] n .
• silylated sulfonic acids such as trimethylsilyl trifluoromethanesulfonate or trimethylsilyl methanesulfonate
• silylated esters of phosphoric acids such as trisphosphoric acid (trimethylsilyl ester) or diethyl trimethylsilyl phosphate are suitable, for example.
• the additives mentioned by way of example according to the invention are used in the process according to the invention in amounts which are at least equivalent to the amount of the catalyst used. 1 to 2 moles of additive per mole of catalyst are preferred.
• the addition is normally carried out at the prevailing reaction temperature; then the reaction mixture thus stopped is cooled to room temperature.
• polyisocyanate mixtures according to the invention can of course be used in a manner known per se with suitable blocking agents for isocyanate groups such as e.g. Phenol, ⁇ -caprolactam, diethyl malonate or ethyl acetoacetate are blocked.
• suitable blocking agents for isocyanate groups such as e.g. Phenol, ⁇ -caprolactam, diethyl malonate or ethyl acetoacetate are blocked.
• polyisocyanate mixtures according to the invention or their derivatives obtained by the blocking reaction mentioned are valuable starting materials for the production of polyurethane plastics by the isocyanate polyaddition process.
• the polyisocyanate mixtures according to the invention from the diphenylmethane series with a content of higher functional proportions, preferably for the production of polyurethane foams, in particular for the production of essentially closed-cell rigid foams containing urethane, urea, biuret, isocyanurate and carbodiimide groups, and very particularly preferably for Use the production of appropriate water-driven, CFC-free rigid foams with improved fire behavior.
• the following exemplary embodiments explain the invention.
• Example 1 2.08 kg of isocyanate mixture 3 were reacted with 1.2 g (0.5 mmol) of catalyst solution for 4 1/2 hours (25 l of CO 2 ) and with 2.1 g of catalyst solution (0.9 mmol) ( 10% in diisopropyl ether) stopped. A liquid, storage-stable polyisocyanate mixture was obtained, the carbodiimide groups of which were largely converted into uretonimine groups after 15 days of storage at room temperature. NCO: 26.1% Viscosity (23 ° C): 900 mPas
• Example 2 was repeated and quenched with 0.12 g of butyl carbamic acid chloride (0.9 mmol).
• the product constantly developed CO 2 (pressure build-up) so that it had to be discarded after 15 days with an increasing viscosity of 1600 mPas.
• a storage-stable, liquid polyisocyanate was obtained which, after 15 days of storage at room temperature, had largely uretonimine groups, with the data: NCO: 28.7% Viscosity: 60 mPas
• Example 1 of DE-OS 2 537 685 was repeated. Although the catalyst: stopper ratio was 1:30, pointed after 15 days of storage the product has comparatively poorer values: NCO: 27.8% Viscosity (23 ° C): 90 mPas
• Example 1 was repeated with 0.08 g of catalyst (0.7 mmol). After 5 hours, 40 l of CO 2 had been split off. The mixture was diluted with 2.08 kg of isocyanate mixture 1 and stopped with 0.4 g (1.3 mmol) of tris phosphoric acid (trimethylsilyl ester). NCO: 27.0% Viscosity (23 ° C): 400 mPas (after 10 days at room temperature)
• Table 1 below lists foam formulations using the liquid polyisocyanate mixture according to the invention (Example 1 / Example a).
• Comparative example c) contains an appropriate prepolymer as the NCO component.
• the resulting CFC-free rigid foams are produced in a manner known per se.
• Table 2 Test results fire behavior fire behavior (according to DIN 4102) Examples from Table 1 Edge flaming sample Reaching the measuring mark 150 mm (s) Example a) 1 x 2nd x 3rd x 4th x 5 x Example b) (comparison) 1 9 2nd 10th 3rd 10th 4th 9 5 10th Example c) (comparison) 1 7 2nd 8th 3rd 7 4th 7 5 7 x ⁇ Measuring mark not reached
• Examples b) and c) (comparative examples) fail the edge flame test. Their fire behavior is therefore significantly less favorable and can be classified as "easily flammable”.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Polyurethanes Or Polyureas (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Applications Claiming Priority (2)

Publications (3)

Family

ID=6432593

Family Applications (1)

Country Status (8)

Families Citing this family (36)

Family Cites Families (3)

• 1991
  • 1991-05-28 DE DE4117384A patent/DE4117384A1/de not_active Withdrawn
• 1992
  • 1992-05-15 AT AT92108269T patent/ATE155460T1/de not_active IP Right Cessation
  • 1992-05-15 EP EP92108269A patent/EP0515933B1/de not_active Expired - Lifetime
  • 1992-05-15 DE DE59208702T patent/DE59208702D1/de not_active Expired - Lifetime
  • 1992-05-15 ES ES92108269T patent/ES2103853T3/es not_active Expired - Lifetime
  • 1992-05-18 US US07/884,143 patent/US5202358A/en not_active Expired - Lifetime
  • 1992-05-25 CA CA002069384A patent/CA2069384C/en not_active Expired - Fee Related
  • 1992-05-26 JP JP15739692A patent/JP3236348B2/ja not_active Expired - Lifetime
  • 1992-05-26 KR KR1019920008896A patent/KR100216934B1/ko not_active IP Right Cessation

Also Published As

Similar Documents

Legal Events